A STUDY  OF  OXAZOLON  AND  PENTOXAZOLON  RINGS  AND 
THEIR  DECOMPOSITION  PRODUCTS 


BY 

CHARLES  WILLIAM  RODEWALD 


THESIS 


Submitted  in  Partial  Fulfillment 
of  the  requirements  for  the 
Degree  of 

MASTER  OF  SCIENCE 
IN  CHEMISTRY 

IN 

THE  COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 

OF  THE 

UNIVERSITY  OF  ILLINOIS 


1921 


* 


\ 'O 

UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


July  .30,  192l_ 


I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 
SUPERVISION  BY Charles  7illiara  Hodev/ald 

ENTITLED  A study  ^'TTcyAZQT  rvT  


D^COirQCTTICTT  ^OTXTCTS. 

BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 
THE  DEGREE  OF  faster  of  Science  in  Chemistry. 


Recommendation  concurred  in* 


Committee 


on 

Final  Examination* 


^Required  for  doctor’s  degree  but  not  for  master’s 


47698? 


■ 


ACMOWLEDGMSETT . 

The  writer  desires  to  take  this  opportunity 
to  express  his  appreciation  of  the  guidance  and  help 
given  by  Dr.  Roger  Adams  in  the  preparation  of  this 
the  si  s . 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/studyofoxazolonpOOrode 


IXTD3X 


Fage . 

A STUDY  OF  OXAZQLOII  AIO  EMTOEAZOLOII  RINGS  AETD  THEIR  DECOH* 


POSITION  PRODUCT 3. 

Introduction  . . 

Historical 

Theoretical 
Experimental . . . 
TIE  USE  OF  CHLORAMINE  T 
AGEUT3. 


1 

2 

3 

5 


DIOHLORAMINH  T v:  0 HLOE IN  AT IH G 


Introduction 9. 

historical . . 10. 

Theoretical 11. 

Experimental ....  12 . 

A STUDY  OF  COMPOUNDS  SIMILAR  TO  D K. 

Introduction 15. 

Theoretical 16. 

Experimental 17 . 


THE  R 1PARATI0K  OF  TROPIC  ACID  BY  THE  REDUCTION  OF  FORMYL 


PHEUYL  ACETIC  ESTER. vl 


20 


*T  ’ 


2 


HISTORICAL. 

There  has  not  been  a great  deal  of  work  published  on  oxazolon 
and  pentoxazolon  ring  compounds. 

ITemirowshy  made  >S-chlore thy  1 chlor  carbonate  from  phosgene  and 
ethylene  chlorhydrin.  3 y condensing  this  with  aniline,  he  made  the 
yS- chlor  ethyl  ester  of  phenyl  carbaminic  acid.  Je  then  made  H-phenyl 
oxazolon  by  treating  the  ester  with  alhali. 

Otto"-  made  '7-phenyl  oxazolon  in  a different  way.  TJe  condensed  ani- 
line with  ethylene  chlorhydrin  to  fora  hydroxy  ethyl  anilihe  and  then 
treated  this  compound  with  phosgene. 


• ' . * • - 


. 


r • ; 


■ 


3 


TiiGQRGTlCAL. 

Gxazolon  and  pentoxazolon  rings  ars  formed  b:  the  condensation  of 
-chlor  esters  of  chlor  carbonic  acid  with  primary  aromatic  amines. 

The  products  of  this  condensation  are  derivatives  of  carbaminic  acid. 

.hen  these  carbaminic  acid  derivatives  are  treated  with  excess  alkali 
in  solution,  'TCI  splits  out  of  the  side  chain  and  a ring  compound  is 
formed.  hen  chlorethyl  chlor  carbonate  is  used,  the  ring  compound 
formed  is  a derivative  of  oxazolon  and  when  chlorpropyl  chlor  carbonate  is 
used,  the  ring  compound  is  a pentoxazolon  derivative.  The  reactions 
involved  are  as  follows; 

SENHg  +■  Cl-CQ-O-CHh-GHg-Gl  -*•  BHH-CQ-O-  JHg-C  . - Cl 

-t-  iu  . *::ci. 

ThiZ-CO-O-Gh^-CK— Cl  f I'OIf.  - — * hC  \ 

ch2-ch2 

The  amines  used  in  the  preparation  of  the  ring  compounds  were  ani- 
line  and  p-chlor  aniline.  ‘ 

/S -chlorethyl  chlor  carbonate  was  made  by  passing  phosgene  into 
elthylene  chfhorhydrin . r -chlorpr  1 chlor  carbonate  was  made  by  passing 

phosgene  into  trimethylene  chlorhydrin. 

The  condensations  between  the  .romatic  primary  amines  and  the  chlor 
esters  of  chlor  carbonic  acid  were  carried  out  in  water  suspension. 

The  carbaminic  acid  derivatives  thus  formed  were  white  crystalline  solids 
soluble  in  the  ordinary  organic  solvents  and  usually  crystallizable  from 

one  of  them. 

The  formation  of  the  ring  compounds  from  the  carbaminic  acid  deriv- 
atives was  brought  about  by  refluxing  the  latter  with  four  or  five 
moles  of  alkali  in  concentrated  aqueous  solution. 

The  preparation  of  the  amino  alcohols  was  attempted  by  first  isolating 


4. 


the  ring  compounds  and  then  hydro li zing  them;  and  also  by  prolonged  treat- 
ment of  the  carbaminic  acid  derivatives  with  KOH  solution. 


"XPERIIOTTAA. 

..reparation  of  /^-chlorpropyl  Chlor  Carbonate. 

94  g.  of  teimethylene  chlorhydrin  were  placed  in  a bottle  surrounded 
by  ice  and  salt.  Phosgene  was  passed  through  in  a stream  of  bubbles, 

(slow  enough  to  be  counted)  until  the  weight  remained  constant.  The  in- 
crease in  weight  was  about  80g.  A rather  narrow  bottle  was  used  so  that 
the  phosgene  -ould  have  greater  opportunity  to  react  with  the  chlorhydrin. 
A calcium  chloride  tube  was  used  in  the  tube  carrying  the  gas  out  of  the 
bottle  to  prevent  water  from  getting  into  the  reaction.  About  six  hours 
were  required  to  pass  in  the  phosgene.  After  the  phosgene  was  all  passed 
in,  the  bottle  was  al loved  to  warm  to  room  temperature  and  the  contents 
were  poured  into  a 500  cc . flash  fitted  with  a reflux  condenser  with 
a calcium  chloride  tube  in  the  top.  rvhe  mixture  was  refluxed  for  an 
hour  or  two  until  no  more  HC1  or  COClo  was  given  off.  The  mixture  was 
cooled  and  washed  once  with  a 5f*  solution  of  sodium  carbonate  and  then 
twice  with  distilled  water. 

The  product  was  then  distilled.  Boiling  oint,  178-80.  Yield, 
70-75/!. 

Preparation  of  f -chlorpropyl  Ester  of  p-Chlorphenyl 
Carbaminic  Acid. 

To  lo4  g.  of  p-chlor  amiline,  500  cc.  of  water  are  added.  75  g. 
of /^chlorpropyl  chlor  carbonate  are  added  in  portions  of  5 cc . The 
reaction  mixture  is  shaken  vigorously  after  each  addition.  After  the 
last  of  the  chlorcarbonate  has  been  added,  the  reaction  is  allowed  to 

stand  for  12  hours  or  more.  The  water  layer  is  separated  in  a separatory 
funnel  and  the  oily  layer  poured  out  into  a beaker.  This  is  ashed  with 
a lop  solution  of  HC1.  Upon  washing  wi th  HC1  the  product  becomes  solid. 
It  is  filtered  off,  washed  with  v/ater,  and  dissolved  in  300  cc.  of  ether. 


6 


The  ethereal  solution  is  dried  over  calcium  chloride.  150  cc . of  ligroin 
are  added  and  most  of  the  ether  is  evaporated  off  on  the  steam  bath. 

On  cooling,  the  product  crystallizes  out  in  white  needles.  Yield  70^. 
Melting  Point  52-.!  3°. 

In  preparing  the  r -chlorpropyl  ester  of  phenyl  carbaminic  acid  by 
condensing  aniline  with  A chlorpropyl  chlor  carbonate,  difficulty  was 
experienced  in  getting  the  product  in  a crystalline  form.  It  is  necessary 

4 

to  wash  out  all  traces  of  the  aniline  with  dilute  /"Cl. 

Preparation  of  IT  p-Chlorphenyl  Pentoxazolon. 

5 g.  (One  mole) 'of  the  carbaminic  ester  and  5g.  (6  moles)  of  EDH 
were  refluxed  with  50  cc.  of  water  for  one  hour.  The  mixture  was  cooled 
and  extracted  w ith  100  cc.  of  benzene.  About  half  of the  benzene  was  evap- 
orated off  and  the  pentoxazolon  was  precipitated,  on  cooling,  by  adding 

ligroin.  The  crystals  were  filtered  off,  dissolved  in  benzene  and  re- 
precipitated. The  product  was  then  dissolved  in  hot  water  and  allowed  to 
crystallize  out.  The  product  should  be  white.  If  highly  colored  it  may 
be  boiled  with  a little  bone  black.  r'he  yield  of  purified  material  was 
45^  of  the  theoretical.  Melting  Point,  113-114°. 

7 reparation  of  the  Amino  Alcohol. 

5 g.  of  the  /"^chlorpropyl  ester-  of  p-chlorphenyl  carbaminic  acid 
were  refluxed  eight  hours  with  5 g.  of  KOH  in  concentrated  acueous  solution, 
in  an  attempt  to  carry  the  reaction  through  to  the  amino  alcohol  without 
isolating  the  pentoxazolon  as  an  intermediate.  The  result  was  a mixture 
of  an  oil  and  a solid.  ITo  definite  compound  was  isolated. 

10  g.  of  II  p-chlorphenyl  pentoxazolon  were  refluxed  for  five  hours 
7/ith  eight  grams  of  KOH  in  75  cc.  of  water.  A heavy  oily  product  resulted. 

It  was  washed  with  water  and  distilled  under  diminished  pressure.  The 
boiling  point  was  205-211  at  18-20  mm.  pressure.  This  was  probably  the 


. 

. 

. 

. 

. 

' . ,i  . 1 ; ■ ; 

' ■ i . 

. 

• , ... 


» . . I 4 


. 


_ . . . ■ 


) 


7 


amino  alcohol.  Cl S GH?- C H?- CH0  OH . rihis  compound  was  not  prepared  in 

sufficient  quantities  for  analysis.  At  this  point  the  supply  of  phosgene 
gave  out  and  the  work  was  abandoned. 

Attempted  ''reparation  of  Phosgene. 

.In  attempt  was  made  to  prepare  phosgene  'rom  CCl^  and  fuming  sulfuric 
acid.  100  cc.  of  CCl^  were  heated  to  brisk  boiling.  A 2 Ft.  air  condenser 
with  a water  condenser  above  was  used  as  a reflux  condenser.  120  cc . 
of  fuming  sulfuric  acid  $20~  excess  SO r/ ) were  allowed  to  flow  slowly  down 
the  condenser.  The  odor  of  phosgene  was  apparent  but  it  was  not  formed 
in  any  qu-ntity.  It  is  probable  that  the  fuming  sulfuric  acid  used  did 
not  contain  3O3  in  sufficient  excess  for  this  preparation. 


,x 

* 

■ V 


' ' 


8 


aomaKY. 

/^■chlorpropyl  chlorcarbonate  will  condense  with  primary  aromatic 
amines  to  form  esters  of  substituted  chlor  carbarainic  acids,  “.'hen  these 
esters  are  refluxed  with  alkalis,  HC1  is  split  out  and  ring  compounds  are 
formed.  ".Tien  these  ring  compounds  are  further  treated  with  alkali,  they 
are  hydrolized,  carbon  dioxide  is  split  out,  and  amino  alcohols  are 
formed. 


* 


• ■ a:  ' 'I-  . • , ' t 


... 


* 


9. 

THE  USE  OF  CHLORAMINE  T AND  DI CHLORAMINE  T AS  CHLORINATING  AGENTS. 

-o- 

INTRODUCTION. 

During  the  war,  facilities  were  developed  for  making  the  N-chlor 
derivatives  of  p-toluene  sulphonamide . They  were  used  as  antiseptics, 
their  antiseptic  action  being  due  to  their  property  of  giving  up  chlorine 
in  the  presence  of  organic  matter.  It  was  thought  that  these  compounds 
might  be  valuable  in  chlorinating  various  organic  compounds  in  cases 
where  the  chlorination  was  more  or  less  difficult  to  control.  It  was 
the  object  of  this  work  to  investigate  the  use  of  these  compounds  as 
chlorinating  agents.  They  ?;ere  tried  out  in  the  chlorination  of  phenol 
and  acetophenone. 


10. 


HISTORICAL. 

nr 

Chloramine  T and  dichloramine  T were  prep  .red  by  Chattaway/'  in  the 
course  of  an  investigation  which  covered  a large  number  of  the  nitrogen 
halogen  derivatives  of  the  sulphonamides . 

Dakin^  has  done  a la-ge  amount  of  work  on  the  p eparation  and  use  of 
chloramine  T and  dichloramine  1 as  antiseptics. 


. 


11 


cWa  THEORETICAL 


cH. 


'3 


Chloramine  T is 


and  dichloramine  T is 


0 


The  former  is  soluble  in  water  and  the  latter  in  various  organic  solvents. 
They  give  up  chlo.  ing  ’quite  readily  to  form  p- toluene  sulphonamide . 

Their  use  as  chlorinating  agents  would  have  an  advantage  in  that  the  exact 
amount  of  chlorine  present  could  b*  determined  and  also  the  addition  of 
chlorine  to  any  reation  mixture  could  be  cade  as  slowly  as  might  be 
desired.  ,lso  the  chlorine  liberated  from  these  compounds,  being  in  a 
somewhat  nascent  state  might  have  some  selective  action  which  free  chlorine 
would  not  possess. 


..  i 


SXPSRIIOSITAI. 


1.2. 


Chlorination  of  Phenol. 

94  ‘g.  of  phenol  were  dissolved,  in  one  liter  of  water.  282  g.  of 
chloramine  T were  added.  The  reaction  was  allowed  to  proceed  at  room 
temperature.  Crystals  of  p-toluene  sulphonamide  soon  began  to  appear. 

After  four  hours  the  solution  was  filtered  and  then  extracted  with  ether 
to  remove  all  of  the  sulphonamide.  168  g.  (97.5^  of  the  theoretical) 
of  crude  p- toluene  sulphonamide  were  recovered.  The  solution  of  phenol 
7/as  alkaline  at  this  point.  It  was  acidified  with  HC1  md  an  oil  separ- 
ated and  settled  to  the  bottom.  This  was  separated  from  the  acueous  layer 
and  distilled.  On  distillation,  20  g.  of  p-chlor  phenol  md  32  g.  of  o- 
chlor  phenol  were  obtained. 

Chlorination  of  Aceto-phenone 

An  attempt  was  made  to  use  dichlorarnine  n in  alcoholic  solution 
but  the  solution  in  alcohol  was  entirely  too  unstable  and  on  exposure 
to  sunlight  or  on  slight  heating,  chlorine  was  rapidly  evolved. 

50  g.  of  aceto  phenone  were  pi  ced  in  a flash  fitted  with  a reflux 
condenser  and  heated  to  80°  in  the  direct  sunlight.  58  g.  of  dichloramine 
T iissolved  in  250  cc.  of  benzene  were  then  added  in  a slow  stream  through 
a separatory  funnel.  The  solution  was  kept  boiling.  The  solution  of 
dichlorarnine  T in  benzene  must  be  kept  cool  or  chlorine  will  be  evolved. 

The  refluxing  was  continued  for  n hour  after  the  addition  of  the  chlor- 
amine. 125  cc.  of  benzene  were  distilled  off  and  the  mixture  cooled  in 
ice  md  salt.  p-Toluene  sulphonamide  crystallized  out  and  was  filtered 
off,  and  washed  with  a little  cold  benzene.  The  filtrate  and  benzene 

washings  were  washed  t-  ice  with  a cold  solution,  (10 f.)  of  ITaOH.  The  sol- 
ution was  then  dried  over  calcium  chloride.  Part  of  the  benzene  was  dis- 
tilled off  and  -chlor  aceto  phenone  crystallized  out.  Yield,  40"  . 


• ’ L 


■S'. 

. 

. 

. 

. 

- 

. ' 

. . . 

' ' 


# 


; • . J 


, 

. . r ' ■ y 

-•c  r r. . ...  1 .>  t i 


... 

•• 

■ ..  • 


. 


. " . . - 


i.  ■ T • 

,-J 


15 


Friedel  and.  Craft’s  reaction  'ith  Dichloramine  T. 


It  was  thought  that  it  might  be  possible  to  form  the  IT-diphenyl 
derivative  of  toluene  p-sulphonamide  by  treating  dichloramine  T with 
benzene  in  the  p esence  of  AlCl*; 


75  g.  of  AlCljj  and  200  cc.  of  benzene  were  placed  in  a one  liter 
flask.  A solution  of  120  g.  of  dichloramine  T in  200  cc.  of  benzene 
was  added  in  small  portions.  There  was  quite  a vigorous  reaction,  in 
which  chlorine  was  given  off.  The  reaction  was  allowed  to  proceed  at 
room  temperature,  '.'/hen  the  reaction  had  subsided,  the  mixture  was  re- 
fluxed for  hours.  The  reaction  mixture  was  pjrared  out  into  cold  water 

and  divided  into  t :o  portions.  One  portion  was  acidified  with  sulfuric 
acid  and  steam  distilled.  Benzene,  monochlor  benzene,  and  toluene  p- 
sulphonamide  were  obtained  in  the  distillation.  The  other  portion  was 
made  strongly  alkaline  with  PaOH  and  steam  distilled.  Benzene  and  mono- 
chlor benzene  came  over.  In  all,  51  g.  of  monochlor  benzene  and  259 
g.  of  benzene  were  obtained  In  the  distillation,  indicating  that  none  of 
the  benzene  had  reacted  with  the  dichloramine  T to  give  the  compound 
desired. 


14 


"ULEklARY . 

Chloramine  T and  dichloramine  T were  used  respectively  in  the 
chlorination  of  phenol  and  of  acetophenone.  Chlorination  with  these  rea- 
gents sh07/ed  no  particular  advanta  e over  the  use  of  free  chlorine. 

An  unsuccessful  attempt  was  made  to  prepare  the  IT-diphenyl  derivative 
of  toluene  j^-sulphonamide  hy  treating  dichloramine  T with  benzene  in  the 
presence  of  AlCl^. 


. ' 


: 


15. 


A STUDY  OF  COMPOUNDS  SIMILAR  TO  D M. 

During  the  war  the  compound  <0  , known  as  D M,  was  made 

^ A*'C/ 

by  condensing  diphenyl  amine  with  arsenic  trichloride.  It  was  thought 
that  similar  compounds  mi^it  be  made  by  condensing  other  compounds  con- 
taining two  phenyl  groups  with  arsenic  trichloride.  Tn  this  work  such 

■v 

condensations  were  attempted  with  carbazole,  benzidine,  phenanthrene,  and 
diphenyl . 


16 


THEORETICAL. 

The  condensation  product  between  AsCl^  and  diphenyl  amine  was  easily 
obtained  by  merely  treating  the  dipnehyl  amine  with  the  chloride  either 

with  or  without  a solvent.  In  the  cases  where  a solvent  had  been  used, 
the  solvent  was  xylene.  The  reaction  was  as  follows: 

O-w-o  ^ t-zt/c/ 

i'-c/ 

In  the  present  work,  each  of  the  substances  used  was  tried  in  xylenfc 
solution,  and  without  a solvent,  and  in  every  case  without  and  with  AlCl* 
as  a catalytic  agent.  There  were  no  indications  of  condensation  in  any 
case.  In  all  instances  where  no  solvent  was  used,  the  mass  carbonized 
when  heated  with  A1C1*  and  the  result  was  merely  ch  rcoal. 


' 


17. 


EXPBEIBMTAL. 

Condensation  of  Arsenic  Trichloride  with  Carbazole. 

12  g.  of  sublimed  cargazole  were  laced  in  a small  flash  with  13.5  g. 
of  A1C1-  and  heated  in  afc  oil  bath  at  170-180°  for  four  and  one-half 
hours.  The  reaction  mixture  was  poured  into  water  and  a small  amount  of 
rTCl  added.  The  solid  which  separated  on  firing  the  mixture  into  water 

was  filtered  off.  It  was  unchanged  carbazole. 

24  g.  of  carbazole  were  dissolved  in  175  cc.of  xylene.  27  g.  of  AsClg 
were  added  and  the  mixture  refluxed  for  five  hours.  Tiere  was  no  reaction 
as  shown  bp  the  fact  that  no  HC1  was  evolved.  19  g.  of  AICI3  were  added 
and  the  mixture  was  again  refluxed.  A solid  began  to  separate  out. 

After  about  20  hours  no  more  101  was  evolved.  Tie  reaction  was  cooled 
and  poured  out  into  cold  water.  A little  HC1  was  added  and  the  mixture 
filtered.  The  solid  product  was  washed  with  ether  by  grinding  in  a mor- 
tar unde:  ether.  The  ether  was  filtered  off.  The  product  proved  to  be 
carbon. 


AsCl'r,  AlCl^  and  carbazole  were  also  heated  together  in  molecular 
propo  tions  without  a solvent,  In  this  case  also  the  mixture  carbonized. 
Condensation  of  Arsenic  Trichloride  with  Benzidine. 

Practical  benzidine  was  purified  by  dissolving  in  the  theoretical 

amount  of  20  HC1  and  then  precipitating  with  ITaOH.  The  substance  thus 
obt  ined  was  dried  in  an  electric  furnace  at  90-100°. 

20'-.  of  benzidine  were  heated  on  an  oil  b..:th  at  150°  with  20  g.  of 
AsCl^  for  four  hours.  The  mixture  was  then  treated  with  150  cc.  of  water 

and  2 cc.  of  concentrated  HC1  were  added.  The  arsenic  was  precipitated 
while  hot,  with  H?S.  The  As  was  filtered  off  and  the  filtrate  made 
alkaline  with  ITaOH.  There  w s a copious  precipitate  whi  h proved  to  be 
benzidine.  Melting  ~oint  124-135°.  It  was  soluble  in  TJC1  and  insoluble 


* - 

\-  y 

: 


18. 

in  an  excess. 

20  g.  of  benzidine  were  dissolved  in  100  cc.  of  xylene  and  brought  to 
boiling  under  a reflux  condenser.  20  g.  of  AsGl^  were  added  drop  by  drop. 
In  this  case  also  the  benzidine  was  recovered  unchanged. 

The  above  condensations  with  benzidine  were  attenpted  using  Aid., 
as  a catalyst.  In  both  cases  the  mixture  carbonized. 

Oondensati  ns  of  Arsenic  Trichloride  with  I henanthrene 
and  Diphenyl . 

Txactly  similar  reactions  were  attempted  with  diphenyl  and  with 
phenanthrene.  In  all  cases  the  results  were  similar  to  those  obtained 
with  carbazole  and  benzidine. 


. 


19. 


SUmUET. 

Condensations  between  AsClr.  and  various  compounds  containing  two 
phenyl  groups  were  tried.  Tt  mi ght  he  expedted  that  two  moles  of  7 Cl 
would  be  split  out  giving  a five  or  a six  membered  ring  with  an  arsenic 
atom  in  the  ring.  Che  condensation  -as  tried  with  carbazole,  benzidine, 
phenanthrene , and  diphenyl.  nhere  was  no  condensation  in  any  case. 


- - i . 

* ' - -*•  T • . ! . . • 


20 


THE  PREPARATION  OF  TROPIC  ACID  BY  THE  CATALYTIC  REDUCTION 
OF  FORMYL  PHENYL  ACETIC  ESTER. 

7/islicen.us  has  prepared  tropic  acid  by  the  reduction  of  phenyl  formyl 
acetic  ester  with  sodium  amalgam.  r,he  object  of  this  research  ■”•••. s to 
perform  the  reduction  catalytically  using  hydrogen  as  the  reducing  agent 
and  platinum  black  as  the  c talyst. 

The  ethyl  ester  of  formyl  phenyl  acetic  acid  was  prepared  b^r  the 

5 

same  method  used  by  "lslicenus  for  tne  preparation  of  the  methyl  ester. 
;thyl  formate  was  used  instead  of  methyl  formate  and  ethyl  phenyl  acetate 
instead  of  the  methyl  ester.  he  yield  was  39  r of  the  theoretical. 

The  boiling  point  was  157-165  at  30  mm. 

10  g.  of  the  formyl  phenyl  acetic  ester  were  dissolved  in  7o  cc. 
of  alcohol  and  shaken  for  36  hours  with  one  gram  of  platinum  black  in  an 
atmosphere  of  hydrogen  under  30  lbs.  pressure  per  square  inch.  ITo 
reduction  took  place.  This  was  shown  by  the  fact  that  no  hydrogen  was 
absorbed,  the  pressure  remaining  constant  throughout  the  entire  time. 


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■Vi 


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21 


BIBLIOGRAPHY. 


1.  J.  : r.  Chen.  (2)  31,  174. 

2.  J.  Pr.  Chen.  (2)  44,  17. 

3.  J.  Chem.  Soc.  87,  145. 

4.  3aMn  £ Bunham:  Handbook  of  Anti septios,  28-47. 

5.  Ann. , 415,  229. 


